EP0033011A1 - Mischungen von Polyarylaten und Polyetherimiden - Google Patents
Mischungen von Polyarylaten und Polyetherimiden Download PDFInfo
- Publication number
- EP0033011A1 EP0033011A1 EP80108183A EP80108183A EP0033011A1 EP 0033011 A1 EP0033011 A1 EP 0033011A1 EP 80108183 A EP80108183 A EP 80108183A EP 80108183 A EP80108183 A EP 80108183A EP 0033011 A1 EP0033011 A1 EP 0033011A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- carbon atoms
- composition
- formula
- bis
- alkylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 C1C2C1C*C2 Chemical compound C1C2C1C*C2 0.000 description 7
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/905—Polyphenylene oxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/928—Polyimide or polyamide-acid formed by condensation of a polyamine with a polycarboxylic acid having at least three carboxyl groups or derivatives thereof
Definitions
- compositions comprising blends of a polyarylate derived from a dihydric phenol and a dicarboxylic acid,and a polyetherimide.
- the compositions can also contain thermoplastic polymers compatible with the blends of polyarylate and polyetherimide.
- Polyarylates are aromatic polyesters derived from a dihydric phenol, particularly 2,2-bis-(4-hydroxyphenyl)- propane (also identified as Bisphenol-A) and an aromatic dicarboxylic acid, particularly mixtures of terephthalic and isophthalic acids.
- Polyarylates are high temperature, high performance thermoplastic polymers with a good combination of thermal and mechanical properties. They have a high continuous use temperature of about 130°C, and good unnotched tough- I ness, with a pendulum impact value of greater than 300 ft. ; lbs./in. 3 . Additionally, polyarylates have inherent fl am - mability and combustion resistance as well as good weatherability. The polyarylates have good melt stability at high temperatures and good color retention. They also have good processability which allows them to be molded into a variety of articles.
- compositions containing polyetherimide and polyarylate yields compositions which have significantly improved environmental stress crack resistance. Also, the compositions containing polyetherimide and polyarylate have excellent mechanical compatibility over the entire range and have excellent mechanical properties. Further, addition of the polyarylate to the polyetherimide results in improved impact strength of the polyetherimide.
- thermoplastic polymer which is compatible with the blend of polyarylate and polyetherimide is added to said blend, the resulting blends possess an acceptable balance of mechanical properties.
- the molding composition of this invention comprises a blend of:
- the polyarylates of this invention are derived from a dihydric phenol and an aromatic dicarboxylic acid.
- a particularly desirable dihydric phenol is of the following formula: wherein Y is independently selected from alkyl groups of 1 to 6 carbon atoms, cycloalkyl grouns of 6 to 12 carbon atoms, aryl groups of 6 to 20 carbon atoms, chlorine or bromine, z has a value of from 0 to 4, inclusive, and R is a divalent saturated aliphatic or aromatic hydrocarbon radical, particularly alkylene and alkylidene radicals having from 1 to 8 carbon atoms, cycloalkylene and cycloalkylidene radicals having up to and including 9 carbon atoms, and arylene radicals having from 6 to 20 carbon atoms.
- dihydric phenols that may be used in this invention include the following:
- dihydric phenols may be used individually or in any combination.
- the preferred dihydric phenol is 2,2-bis(4-hydroxyphenyl)propane.
- dihydric phenols can be used in combination with a dihydric phenol of the following formula: wherein Y and z are as previously defined.
- the aromatic dicarboxylic acids that may be used in this invention include terephthalic acid, isophthalic acid, any of the naphthalene dicarboxylic acids and mixtures thereof, as well as alkyl substituted homologs of these carboxylic acids, wherein the alkyl group contains from 1 to about 4 carbon atoms, and acids containing other inert substituents such as halides, alkyl or aryl ethers, and the like.
- the ratio of isophthalic and terephthalic acids in the mixture is about 20:80 to about 100:0, while the most preferred acid ratio is about 25:75 to about 75:25.
- from about 0.5 to about 20 percent of aliphatic diacids containing from 2 to about 20 carbon atoms, such as adipic acid, sebacic acid, and the like may be additionally used in the polymerization reaction.
- polyester forming reaction can be used to make the polyarylates, such as:
- Two procedures can be used for the preparation of the polyarylates via the acid chloride route. One is carried out at low temperature and the other at high temperature. In the low temperature technique polycondensation of the acid chlorides derived from the dicarboxylic acid(s) with the dihydric phenol(s) is effected at ambient temperatures in an inert solvent, such as methylene chloride, in the presence of a basic catalyst and an acid acceptor. A second immiscible solvent, e.g., water, may be present.
- an inert solvent such as methylene chloride
- polycondensation of acid chlorides with the dihydric phenols is effected in a high boiling solvent, such as 1,2,4-trichlorobenzene, at temperatures above about 150°C and preferably at about 200 to about 220°C.
- a high boiling solvent such as 1,2,4-trichlorobenzene
- Suitable inert organic solvents useful for low temperature polycondensation include halogenated aliphatic compounds, such as, chloroform, methylene bromide, 1,1,2-trichloroethane as well as methylene chloride mentioned above and the like; and cyclic ethers such as tetrahydrofuran, dioxane, and the like.
- suitable solvents include halogenated aromatic compounds such as, o-dichlorobenzene, 1,2,4-trichlorobenzene, diphenyl sulfone, benzoic acid alkyl esters wherein the alkyl group contains 1 to about 12 carbon atoms, phenolic ethers, such as, anisole, diphenyl ether and the like.
- Preferred acid acceptors for use in the low temperature polycondensation are alkali metal and alkaline earth hydroxides including sodium, potassium, barium, calcium, strontium, magnesium, and beryllium hydroxide.
- Useful basic catalysts for use in the low temperature polycondensation include tertiary amines such as alkylamines, including trimethylamine, triethylamine, tripropylamine, tributylamine, and the like; where the alkyl group contains from 1 to about 10 carbon atoms; alkaryl amines such as, N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethylnaphthylamine, benzyl dimethylamine, alpha-methylbenzyl dimethylamine; pyridine, cyclic diazo compounds, such as, diazobicyclooctane (DABCO), diazo bicyclononene (DBN) and diazobicycloundecene (DBU) and the like. Phosphonium, arsonium and similar compounds may also be used as catalysts.
- tertiary amines such as alkylamines, including trimethylamine, triethylamine
- Polymerizations using the Diacetate Process can be carried out in the melt at between 260°C and 340°C, preferably between 275°C and 320°C. They can also be carried out either as a solution reaction at those temperatures or a suspension reaction also at those temperatures.
- the solvent(s) or suspending agent(s) can be one of any number of organic compounds boiling between 140°C and 340°C. They can be chosen from hydrocarbons, ketones, ethers, or sulfones which are inert under the reaction conditions. These polymerizations may or may not be run in the presence of a catalyst. Typical solvents are tetramethylene sulfone, diphenyl ether, substituted diphenyl ether, and the like.
- Typical catalysts include Na, Li, K salts (organic and inorganic), transition metal salts, alkaline earth metal salts, e.g., Mg acetate, and the like. They may be performed at atmospheric pressure, supra atmospheric pressure, or under vacuum.
- Polymerizations using the Diphenate Process can be carried out in the melt at between 285°C and 350°C.
- the preferred temperature range is about 300°C to 340°C.
- reduced pressure for the final portions of the reaction is used. They can also be carried out either as a solution reaction or suspension reaction under those conditions.
- the solvent(s) or suspending agent(s) are the same as those described above.
- Typical catalyst include tin compounds and generally are those mentioned above for the diacetate process. Particularly preferred catalysts are Ti and Sn salts, Mg acetate, and alkali and alkaline earth metal salts, alkoxides and phenoxides.
- polyarylates have a reduced viscosity of from about 0.4 to about 1.0 as measured in chloroform at 25°C (0.2g/100 ml.) or other suitable solvents at suitable temperatures.
- polyetherimides suitable for use in this invention are well known in the art and are described in, for example, U.S. Patents 3,847,867, 3,838,097 and 4,107,147.
- polyetherimides are of the following formulae: wherein a is an integer greater than 1, preferably from about 10 to about 10,000 or more, -0-R 2 -O- is attached to the 3 or
- polyetherimides are prepared by methods well known in the art as set forth in, for example, U.S. Patents 3,833,544, 3,887,588, 4,017,511, 3,965,125 and 4,C24,110.
- the polyetherimides of Formula (I) can, for example, be obtained by any of the methods well-known to those skilled in the art including the reaction of any aromatic bis(ether anhydride)s of the formula where R 2 is as defined hereinbefore,with a diamino compound of the formula where R 3 is as defined hereinbefore.
- the reactions can be advantageously carried out employing well- known solvents, e.g., o-dichlorobenzene, m-cresol/toluene, N,N-dimethylacetanide, etc., in which to effect interaction between the dianhydrides and the diamines, at temperatures of from about 20 to about 250°C.
- the polyetherimides can be prepared by melt polymerization of any dianhydride of Formula III with any diamino compound of Formula IV while heating the mixture of the ingredients at elevated temperatures with concurrent intermixing.
- melt polymerization temperatures between about 200° to 400°C and preferably 230° to 300°C can be employed. Any order of addition of chain stoppers ordinarily employed in melt polymerization can be employed.
- the conditions of the reaction and the proportions of ingredients can be varied widely depending on the desired molecular weight, intrinsic viscosity, and solvent resistance.
- polyetherimides of Formula I have an intrinsic viscosity [ ⁇ ] greater than 0.2 deciliters per gram, preferably 0.35 to 0.60, or 0.7 deciliters per gram or even higher when measured in m-cresol at 25°C.
- aromatic bis(ether anhydride)s of Formula III include, for example,
- the organic diamines of Formula IV include, for example,
- the polyetherimides of formula (II) may, for example, be prepared by effecting reaction in the presence of a dipolar aprotic solvent of a mixture of ingredients comprising, for instance, (1) a bis(nitrophthalimide) of the general formula: wherein R 3 is defined as hereinabove, and (2) an alkali metal salt of an organic compound of the general formula: wherein M is an alkali metal and R 2 is defined as hereinabove.
- the bis(nitrophthalimide) used in preparing the polymer is formed by reacting a diamine of the formula described above with a nitro-substituted aromatic anhydride of the formula:
- the molar ratio of diamine to anhydride should ideally be about 1:2 respectively.
- the initial reaction product is a bis(amide-acid) which is subsequently dehydrated to the corresponding bis(nitrophthalimide).
- nitrophthalic anhydrides useful in the present invention are 3-nitrophthalic anhydride, 4-nitrophthalic anhydride and mixtures thereof. These reactants are commercially available in reagent grade. They may also be prepared by the nitration of phthalic anhydride using procedures described in Organic Syntheses, Collective Vol. I, Wiley (1948), page 408. Certain other closely related nitroaromatic anhydrides may also be used in the reaction and are illustrated for example by 2-nitronaphthalic anhydride, 1-nitro-2,3-naphthalenedicarboxylic anhydride and 3-methoxy-6-nitrophthalic anhydride, and the like.
- alkali metal salts of formula VI among the divalent carbocyclic aromatic radicals which R 2 may represent are, for instance, divalent aromatic hydrocarbon radicals of from 6 to 20 carbon atoms, such as phenylene, biphenylene, naphthylene, etc. Included are residues of, e.g. hydroquinone, resorcinol, chlorohydroquinone, etc.
- R 2 may be a residue of a dihydroxy diarylene compound in which the aryl nuclei are joined by either an ; aliphatic group, a sulfoxide group, sulfonyl group, sulfur, carbonyl group, oxygen, the ⁇ C(CH 3 )(CH 2 ) 2 (COOH) group, ; etc.
- Typical of such diarylene compounds are the following:
- dialkali metal salts of formula VI When dialkali metal salts of formula VI are used with the compound illustrated by formula V, the ingredients are advantageously present in an equal molar ratio for optimum molecular weight and properties of the polymer. Slight molar excesses, e.g., about 0.001 to 0.10 molar excess of either the dinitro-substituted organic compound or of the dialkali metal salt of formula may be employed. When the molar ratios are approximately equal, the polymer is substantially terminated by a - Z-N0 2 at one end and a a phenolic group at the other end. If there is a molar excess of one compound, that particular terminal group will predominate.
- the conditions of reaction whereby the alkali-metal salt of formula IV is reacted with the dinitro-substituted organic compound of formula III can be varied widely. Generally, temperatures of the order of about 25-150°C are advantageously employed, although it is possible to employ lower or higher temperature conditions depending on the ingredients used, the reaction product sought, time of reaction, solvent employed, etc. In addition to atmospheric pressure, superatmospheric pressures and subatmospheric pressures may be employed depending upon the other conditions of reaction, the ingredients used, the speed at which it is desired to effect reaction, etc.
- the time of reaction also can be varied widely depending on the ingredients used, the temperature, the desired yield, etc. It has been found that times varying from about 5 minutes to as much as 30 to 40 hours are advantageously employed to obtain the maximum yield and desired molecular weight.
- the reaction product can be treated in the appropriate manner required to effect precipitation and/or separation of the desired polymeric reaction product.
- common solvents such as alcohols (e.g. methanol, ethanol, isopropyl alcohol, etc.) and aliphatic hydrocarbons (e.g. pentane, hexane, octane, cyclo- hexane, etc.) may be employed as precipitants for this purpose.
- the polymerization is performed under anhydrous conditions usually using dipolar aprotic solvents such as dimethylsulfoxide which are added in varying amounts depending upon the particular polymerization.
- dipolar aprotic solvents such as dimethylsulfoxide which are added in varying amounts depending upon the particular polymerization.
- a total quantity of solvent, dipolar aprotic solvent or mixture of such solvent with an aromatic solvent sufficient to give a final solution containing 10-20% by weight of polymer is preferably employed.
- the preferred polyetherimides include those of the formula:
- thermoplastic polymers which are compatible with the blend of polyarylate and polyetherimide include, polyesters, polycarbonates and poly(aryl ether)s.
- polyesters which are suitable for use herein are derived from an aliphatic or cycloaliphatic diol, or mixtures thereof,containing from 2 to about 10 carbon atoms and at least one aromatic dicarboxylic acid.
- the polyesters which are derived from an aliphatic diol and an aromatic dicarboxylic acid have repeating units of the following general formula: wherein n is an integer of from 2 to 4.
- polyesters are poly(ethylene terephthalate) and poly(1,4-butylene terephthalate).
- polyesters with minor amounts, e.g., from 0.5 to about 2 percent by weight, of units derived from aliphatic acids and/or aliphatic polyols, to form copolyesters.
- the aliphatic polyols include glycols such as poly(ethylene glycol). These can be made following the teachings of, for example. U.S. Patents 2,465,319 and 3,047,539.
- the units which can be present in the copolyesters are those derived from aliphatic dicarboxylic acids, e.g., of up to and above about 50 carbon atoms, including cycloaliphatic straight and branched chain acids, such as adipic acid, cyclohexanediacetic acid, dimerized C 16 -C 18 unsaturated acids (which have 32 to 36 carbon atoms), trimerized acids, and the like.
- aliphatic dicarboxylic acids e.g., of up to and above about 50 carbon atoms
- cycloaliphatic straight and branched chain acids such as adipic acid, cyclohexanediacetic acid, dimerized C 16 -C 18 unsaturated acids (which have 32 to 36 carbon atoms), trimerized acids, and the like.
- polyesters which art derived from a cycloaliphatic diol and an aromatic dicarboxylic acid are prepared by condensing either the cis- or trans-isomer (or mixtures thereof) of, for example, 1,4-eyclohexanedimethanol with the aromatic dicarboxylic acid so as to produce a polyester having recurring units having the following formula: wherein the 1,4-cyclohexane dimethanol is selected from the cis- and trans-isomers thereof and R 10 represents an aryl radical containing 6 to 20 carbon atoms and which is the decarboxylated residue derived from an aromatic dicarboxylic acid.
- aromatic dicarboxylic acids indicated by R 10 in the formula above include isophthalic or terephthalic acid, 1,2-di(p-carboxyphenyl)ethane, 4,4'-dicarboxydiphenyl ether, etc., and mixtures of these. All of these acids contain at least one aromatic nucleus. Fused rings can also be present such as in 1,4- or 1,5-naphthalene-dicarboxylic acids.
- the preferred dicarboxylic acid is terephthalic acid or mixtures of terephthalic and isophthalic acid.
- a preferred polyester may be derived from the reaction of either the cis- or trans-isomer (or a mixture thereof) of 1,4-cyclohexanedimethanol with a mixture of iso- and terephthalic acids. These polyesters have repeating units of the formula:
- Another preferred polyester is a copolyester derived from a cyclohexane dimethanol. an alkylene glycol and an aromatic dicarboxylic acid.
- These copolyesters are prepared by condensing either the cis- or trans-isomer (or mixtures thereof) of, for example, 1,4-cyclohexanedimethanol and an alkylene glycol with an aromatic dicarboxylic acid so as to produce a copolyester having repeating units of the following formula: wherein the 1,4-cyclohexane dimethanol is selected from the c i s- and trans-isomers thereof, R 10 is as previously defined, n is an integer of 2 to 4, the c units comprise from about 10 to about 90 percent by weight, and the d units comprise from about 10 to about 90 percent by weight.
- the preferred copolyester may be derived from the reaction of either the cis- or trans-isomer (or mixtures thereof) of 1,4-cyclohexanedimethanol and ethylene glycol with terephthalic acid in, for example, a molar ratio of 1:2:3.
- These copolyesters have repeating units of the following formula: wherein c and d are as previously defined.
- polyesters as ascribed berein are either commercially available or can be produced by methods well known in the art such as those set forth in, for example, U.S. patent 2,901,466.
- the preferred polyesters are poly (1,4-cyclohexanedimethanol tere/iso-phthalate) and a copolyester of 1,4-cyclohexanedimethanol, ethylene glycol and terephthalic acid and poly(ethylene terephthalate) as previously described.
- polyesters used herein have an intrinsic viscosity of at least about 0.4 to about 2.0 dl/g. measured in a 60:40 phenol/tetrachloroethane mixture or similar solvent at 23-30°C.
- thermoplastic aromatic polycarbonates that can be employed herein are hompolymers and copolymers and mixtures thereof which have an intrinsic viscosity of 0.40 to 1.0 dl./g. as measured in methylene chloride at 25°C. that are prepared by reacting a dihydric phenol with a carbonate precursor.
- Typical of some of the dihydric phenols that may be employed in the practice of this invention are (2,2-bis(4-hydroxyphenyl)propane), bis(4-hydroxyphenyl) methane, 2.2-bis(4-hydroxy-3-methylphenyl) propane, 4,4- bis(4-hydroxyphenyl)heptane, 2,2-(3,5,3',5'-tetrachloro-4,4'-dihydroxydiphenyl)propane, 2,2-(3,5,3',5'-tetrabromo-4,4'-dihydroxydiphenyl)-propane, (3,3'-dichloro-4,4'-dihydroxydiphenyl)methane.
- Other dihydric phenols of the bisphenol type are also useful and are disclosed in U .S. Pat. Nos. 2,999,835, 3,028,365 and 3,334,154.
- the carbonate precursor may be either a carbonyl halide, a carbonate ester or a haloformate.
- the carbonyl halides which can be employed herein are carbonyl bromide, carbonyl chloride and mixtures thereof.
- Typical of the carbonate esters which may be employed herein are diphenyl carbonate, di-(halophenyl) carbonates such as di-(chlorophenyl) carbonate, di-(bromophenyl) carbonate, di-(trichlorophenyl) carbonate, di-(tribromophenyl) carbonate, etc., di-(alkylphenyl) carbonates such as di(tolyl) carbonate, etc., di-(naphthyl) carbonate, di-(chloronaphthyl) carbonate, phenyl tolyl carbonate, chlorophenyl chloronaphthyl carbonate, etc.
- haloformates suitable for use herein include bis-haloformates of dihydric phenols (for example, bischloroformates of bisphenol-A,of hydroquinone, etc.) or glycols (for example, bishaloformates of ethylene glycol, neopentyl glycol, polyethylene glycol, etc.). While other carbonate precursors will occur to those skilled in the art, carbonyl chloride, also known as phosgene, is preferred.
- the aromatic carbonate polymers of this invention may be prepared by using phosgene or a haloformate and by employing a molecular weight regulator, an acid acceptor and a catalyst.
- the molecular weight regulators which can be employed in carrying out the process of this invention include monohydric phenols such as phenol, para-tertiary- butylphenol, para-bromophenol, primary and secondary amines, etc.
- a phenol is employed as the molecular weight regulator.
- a suitable acid acceptor may be either an organic or an inorganic acid acceptor.
- a suitable organic acid acceptor is a tertiary amine and includes such materials as pyridine, triethylamine, dimethylaniline, tributyl- amine, etc.
- the inorganic acid acceptor may be one which ! can be either a hydroxide, a carbonate, or a bicarbonate, of an alkali or alkaline earth metal.
- the catalysts which are employed herein can be any of the suitable catalysts that aid the polymerization of bisphenol-A with phosgene.
- Suitable catalysts include tertiary amines such as, for example, triethylamine, tripropylamine, N,N-dimethylaniline, quaternary ammonium compounds such as, for example, tetraethylammonium bromide, cetyl triethyl ammonium bromide, tetra-n-heptylammonium iodide, tetra-n-propyl ammonium bromide, tetramethylammonium chloride, tetra-methyl ammonium hydroxide, tetra-n-butyl ammonium iodide, benzyltrimethyl ammonium chloride and quaternary phosphonium compounds such as, for example, n-butyltriphenyl phosphonium bromide and methyl-triphenyl
- the polycarbonates can be prepared in a one-phase (homogeneous solution) or two-phase (interfacial) systems when phosgene or a haloformate are used. Bulk reactions are possible with the diarylcarbonate precursors.
- Tie poly(aryl ether) resin may te described as a linear thermoplastic polyarylene polyether wherein the arylene units are interspersed with ether, sulfone or ketone linkages.
- These resins may be obtained by reaction of an alkali metal double salt of a dihydric phenol and a dihalobenzenoid or dinitrobenzenoid compound, either or both of which contain a sulfone or a ketone linkage, i.e., -S0 2 - or -CO-, between arylene groupings, to provide sulfone or ketone units in the polymer chain in addition to arylene units and ether units.
- the polymer has a basic structure composed of recurring units of the formula wherein E is the residuum of the dihydric phenol and E' is the residuum of the benzenoid compound having an inert electron withdrawing group in at least one of the positions ortho and para to the valence bonds; both of said residua are valently bonded to the ether oxygens through aromatic carbon atoms.
- aromatic polyethers are included within the class of polyarylene polyether resins described in U.S. Pat. 3,264,536, the disclosure of which is hereby incorporated herein by reference, for the purpose of describing and exemplifying E and E' in more detail.
- the dihydric phenol be a weakly acidic dinuclear phenol such as, for example, the dihydroxy diphenyl alkanes or the nuclear halogenated derivatives thereof, such as, for example, the 2,2-bia(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)2- phenyl ethane, bia(4-hydroxyphenyl)methane, or the chlorinated derivatives containing one or two chlorines on each aromatic ring While these halogenated bisphenolic alkanes are more acidic than the non-halogenated bisphenols and hence alower reacting in this process, they do impart valuable flame resistance to these polymers.
- the dihydric phenol be a weakly acidic dinuclear phenol such as, for example, the dihydroxy diphenyl alkanes or the nuclear halogenated derivatives thereof, such as, for example, the 2,2-bia(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphen
- bisphenols are also highly valuable and preferred. These materials are the bisphenols of a symmetrical or unsymmetrical joininig group, as, for example, ether oxygen I , carbonyl( sulfide (-S-), sulfone , or hydrocarbon residue in which the two phenolic nuclei are joined to the same or different carbon atoms of the residue.
- Such dinuclear phenole can be characterized as having the structure: wherein Ar is an aromatic group and preferably is a phenylene group, A 2 and A 3 can be the same or different inert substituent groups as alkyl groups having from 1 to 4 carbon atoms, halogen atome, i.e.
- R 11 is representative of a bond between aromatic carbon atoms as in dihydroxydiphenyl, or is a divalent radical, including for example, -0-, -S-, -SO-, -S-S, -S02, and divalent hydrocarbon radicals such as alkylene, alkylidene, cycloalkylene, cyclo- alkylidene + ; or the halogen, alkyl, aryl or like substituted alkylene, alkylidene and cycloaliphatic radicals + as well as aromatic radicals and a ring fused to both Ar groups.
- Examples of specific dihydric polynuclear phenols include among others: the bls-(hydroxylphenyl)alkanes such as 2,2-bis-(4-hydroxyphenyl)propane, 2,4'-dihydroxydiphenylmethane, bis-(2-hydroxyphenyl)methane, bis-(4-hydroxyphenyl)-methane, bis(4-hydroxy-2,6-dimethyl-3-methoxyphenyl)methane, 1,1-bis-(4-hydroxyphenyl)ethane, 1,2-bis-(4-hydroxyphenyl)-ethane, 1,1-bis-(4-hydroxy-2-chlorophenyl)ethane, 1,1-bis-(3-methyl-4-hydroxyphenyl)propane, 1,3-bis-(3-methyl-4-hydroxyphenyl)propane, 2,2-bis-(3-phenyl-4-hydroxyphenyl)propane, 2,2-bis-(3-isopropyl-4-hydroxyphen
- these polyarylene polyethers contain recurring groups of the residuum of the dihydric phenol and the residuum of the benzenoid compound bonded through aromatic ether oxygen atoms.
- any dihalobenzenoid or dinitrobenzenoid compound or mixtures thereof can be employed in this invention which compound or compounds has the two halogens or nitro-groups bonded to benzene rings having an electron withdrawing group in at least one of the positions ortho and para to the halogen or nitro-group.
- the dihalobenzenoid or dinitrobenzenoid compound can be either mononuclear where the halogens or nitro-groups are attached to the same benzenoid ring or polynuclear where they are attached to different benzenoid rings, as long as there is an activating electron withdrawing group in the ortho or para position of that benzenoid nucleus.
- Fluorine and chlorine substituted benzenoid reactants are preferred; the-fluorine compounds for fast reactivity and the chlorine compounds for their inexpensive- ness. Fluorine substituted benzenoid compounds are most preferred, particularly when there is a trace of water present in the polymerization reaction system. However, this water content should be maintained below about 1% and preferably below 0.5% for best results.
- any electron withdrawing group can be employed as the activator group in these compounds. It should be, of course, inert under the reaction conditions, tut otherwise its structure is not critical. Preferred are the strong activating groups such as the sulfone group bonding two halogen or nitro substituted benzenoid nuclei as in the 4,4'-dichlorodiphenyl sulfone and 4,4'-di- fluorodiphenyl sulfone, although such other strong with- drawing groups hereinafter mentioned can also be used with equal ease.
- the ring contain no electron supplying groups on the same benzenoid nucleus as the halogen or nitro group; however, the presence of other groups on the nucleus or in the residuum of the compound can be tolerated.
- all of the substituents on the benzenoid nucleus are either hydrogen (zero electron withdrawing), or other groups having a positive sigma * value, as set forth in J. F. Bunnett in Chem. Rev. 49 273 (1951) and Quart. Rev., 12, 1 (1958). See also Taft, Steric Effects in Organic Chemistry, John Wiley & Sons (1956), chapter 13; Chem. Rev., 53, 222; JACS, 74, 3120; and JACS, 75, 4231.
- the activating group can be basically either of two types:
- the polymers may be made with mixtures of two or more dihalobenzenoid or dinitrobenzenoid compounds.
- the E' residuum of the benzenoid compounds in the polymer structure may be the same or different.
- the E' term defined as being the "residuum of the benzenoid compound” refers to the aromatic or benzenoid residue of the compound after the removal of the halogen or nitro group on the benzenoid nucleus.
- the polyarylene polyethers of this invention are prepared by method well known in the art as the sub- stantially equimolar one-step reaction of a double alkali metal salt of dihydric phenol with a dihalobenzenoid compound in the presence of specific liquid organic sulfoxide or sulfone solvents under substantially anhydrous conditions. Catalyst are not necessary for this reaction but the unique I facility of these solvents to promote the reaction to a high molecular weight product has now provided the critical tool necessary to secure sufficiently high molecular weight aromatic ether products useful for services heretofore limited to such products as polyformaldehydes and polycarbonates.
- the polymers are also prepared in a two-step process in which a dihydric phenol is first converted in situ in the primary reaction solvent to the alkali metal salt by the reaction with the alkali metal, the alkali metal hydride, alkali metal hydroxide, alkali metal alkoxide or the alkali metal alkyl compounds.
- the alkali metal hydroxide is employed.
- the dialkali metal salt of the dihydric phenol is admixed and reacted with about stoichiometric quantities of the dihalobenzenoid or dinitrobenzenoid compound.
- the polymerization reaction proceeds in the liquid phase of a sulfoxide or sulfone organic solvent at elevated temperatures.
- a preferred form of the polyarylene polyethers of this invention are those prepared using the dihydric polynuclear phenols of the following four types, including the derivatives thereof which are substituted with inert substituent groups in which the R 13 group represents hydrogen, lower alkyl, lower aryl and the halogen substituted groups thereof, which can be the same or different.
- the system should be substantially anhydrous, and preferably with less than 0.5 per cent by weight water in the reaction mixtures.
- the poly(aryl ether)s have a reduced viscosity of from about 0.4 to about 1.5 as measured in an appropriate solvent at an appropriate temperature depending on the particular polyether, such as in methylene chloride at 25°C.
- the preferred poly(aryl ether)s have repeating units of the formula:
- the polyarylate is used in amounts of from about 95 to about 5 preferably from about 80 to about 20 weight percent.
- the polyetherimide is used in amounts of from about. 5 to about 95 preferably from about 20 to about 80 weight percent.
- the thermoplastic polymer when used, is used in amounts of from about 0 to about 40 preferably from about 0 to 25 weight percent.
- compositions of this invention are prepared by any conventional mixing methods.
- a preferred method comprises mixing the polyarylate and the polyetherimide and optionally, thermoplastic polymer in powder or granular form in an extruder and extruding the mixture into strands, chopping the strands into pellets and molding the pellets into the desired article.
- additives include plasticiters; pigments; flame retardant additives, particularly, decabromodiphenyl ether and triarylphosphates, I such as triphenylphosphate; reinforcing agents, such as glass fibers; thermal stabilizers; ultraviolet light stabilisers, processing aids, impact modifiers and the like.
- Control A was a polyarylate (Ardel D-100, sold by Union Carbide Corporation and prepared from, Bisphenol-A and a mixture of 50 mole percent each of terephthalic and isophthalic acid chlorides, by conventional methods) having a reduced viscosity of 0.66 as measured in p-chlorophenol at 49°C (0.2 g/100 ml.).
- the polyarylate was compression molded at 250°C in a 4X4X0.020 inch cavity mold. 1/8 inch strips were shear cut from the molded product. These strips were tested for 1% secant modulus according to a procedure similar to ASTM-D-638; elongation at break according to ASTM D-638; pendulum impact strength. Also, samples were placed under the stress shown in the Table. A cotton swab saturated with the chemical environment, as identified in the Table, is attached to the center of the test specimen. The time for the specimen to rupture is then recorded. Additionally the clarity of the sample after molding was recorded.
- Control B was a polyetherimide of the following formula:
- This polyetherimide had a reduced viscosity of 0.51 as measured in chloroform (0.5 gm per 100 ml) at 25°C.
- the polyetherimide was compression molded and tested as described in Control A.
- Control A 50 weight percent of the polyarylate of Control A was blended with 50 weight percent of the polyetherimide of Control B in a Brabender blender at about 300°C. The blend was compression molded and tested as described in Control A.
- Control A 25 weight percent of the polyarylate of Control A was blended with 75 weight percent of the polyetherimide of Control B in a Brabender blender at about 300°C. The blend was compression molded and tested as described in Control A.
- Example 15 weight percent of the polyarylate of Control A was blended with 75 weight percent of the polyetherimide of Control B and 10 weight percent of the poly(ethylene terephthalate) of Example 4 in a Brabender blender at about 300°C. The blend was compression molded and tested as described in Example 4.
- 25 weight percent of the polyarylate of Control A was blended with 50 weight percent of the polyetherimide of Control B and 25 weight percent of a polycarbonate (Lexan 143) having a reduced viscosity of 0.57 as measured in chloroform at 25°C (0.5 gr. per 100 ml).
- the blend was compression molded and tested as described in Example 4.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT80108183T ATE13773T1 (de) | 1979-12-26 | 1980-12-23 | Mischungen von polyarylaten und polyetherimiden. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US106504 | 1979-12-26 | ||
US06/106,504 US4250279A (en) | 1979-12-26 | 1979-12-26 | Polyarylate blends with polyetherimides |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0033011A1 true EP0033011A1 (de) | 1981-08-05 |
EP0033011B1 EP0033011B1 (de) | 1985-06-12 |
Family
ID=22311766
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP80108183A Expired EP0033011B1 (de) | 1979-12-26 | 1980-12-23 | Mischungen von Polyarylaten und Polyetherimiden |
Country Status (6)
Country | Link |
---|---|
US (1) | US4250279A (de) |
EP (1) | EP0033011B1 (de) |
JP (1) | JPS5699252A (de) |
AT (1) | ATE13773T1 (de) |
CA (1) | CA1157190A (de) |
DE (1) | DE3070763D1 (de) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0097969A1 (de) * | 1982-06-30 | 1984-01-11 | Amoco Corporation | Plastifiziertes thermoplastisches Polymer |
EP0104659A2 (de) * | 1982-09-29 | 1984-04-04 | Amoco Corporation | Mischungen von Poly(etherimiden) und Polyamiden |
EP0133236A2 (de) * | 1983-07-28 | 1985-02-20 | Bayer Ag | Thermoplastische Formmassen |
EP0594386A1 (de) * | 1992-10-23 | 1994-04-27 | General Electric Company | Duktile Mischungen von Polyestercarbonate oder Polyarylate mit Polyimidharzen |
Families Citing this family (43)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4645804A (en) * | 1981-05-01 | 1987-02-24 | General Electric Company | Polycarbonate/imide hetero group condensation polymer blends |
US4433118A (en) * | 1981-09-11 | 1984-02-21 | Standard Oil Company (Indiana) | Poly (p- and m-methylenebenzoate) blends with polyarylates |
US4908419A (en) * | 1982-01-29 | 1990-03-13 | General Electric Company | Polyetherimide-polyarylate, blends |
US4548997A (en) * | 1982-04-05 | 1985-10-22 | General Electric Company | Polyetherimide-polycarbonate blends |
EP0117326A1 (de) * | 1983-02-25 | 1984-09-05 | General Electric Company | Polyetherimiden-Polyarylaten-Mischungen |
EP0117327A1 (de) * | 1983-02-25 | 1984-09-05 | General Electric Company | Ternäre Polymermischungen |
US4485215A (en) * | 1983-05-11 | 1984-11-27 | Atlantic Richfield Company | Molding composition |
JPS60501413A (ja) * | 1983-05-23 | 1985-08-29 | ゼネラル エレクトリツク カンパニイ | ポリエ−テルイミド−ポリカ−ボネ−トブレンド |
EP0158733A1 (de) * | 1983-12-29 | 1985-10-23 | General Electric Company | Polyetherimid-Polyestercarbonat-Mischungen |
US4673708A (en) * | 1984-12-28 | 1987-06-16 | General Electric Company | Impact modified polyetherimide-polycarbonate blends |
US4687819A (en) * | 1984-12-31 | 1987-08-18 | General Electric Company | Polyterephthalatecarbonate-polyetherimide-polyester blends |
US4835197A (en) * | 1985-01-04 | 1989-05-30 | Raychem Corporation | Aromatic polymer compositions |
JPS62501370A (ja) * | 1985-01-04 | 1987-06-04 | レイケム・コ−ポレイション | ポリイミド主鎖にフェニルインダンジアミンおよび/または二無水物残基を有するポリイミド組成物 |
US4920005A (en) * | 1985-01-04 | 1990-04-24 | Raychem Corporation | Aromatic polymer compositions |
US4879338A (en) * | 1985-02-13 | 1989-11-07 | Raychem Corporation | Poly(aryl ether ketone) compositions |
US4965310A (en) * | 1985-03-27 | 1990-10-23 | Amoco Corporation | Wear resistant poly (aryl ether ketone) polyimide blends |
US5171796A (en) * | 1985-07-23 | 1992-12-15 | Amoco Corporation | Miscible blends of a poly(aryl ether ketone) and an imide containing polymer |
US4629759A (en) * | 1985-10-28 | 1986-12-16 | General Electric Company | Flame retardant polyetherimide-polycarbonate blends |
US5052369A (en) * | 1985-12-13 | 1991-10-01 | Johnson Kendrick A | Heat retaining food container |
US4879354A (en) * | 1986-08-07 | 1989-11-07 | Amoco Corporation | Miscible blends of an amide and/or imide containing polymer and a polyarylate |
EP0256761A3 (de) * | 1986-08-07 | 1989-05-31 | Amoco Corporation | Zusammensetzungen aus Amid- und/oder Imid enthaltendem Polymer und einem Polyarylat |
JPS6372755A (ja) * | 1986-08-07 | 1988-04-02 | アモコ コ−ポレ−シヨン | アミド及び/又はイミド含有重合体とポリアリ−レ−トの相溶性ブレンド |
US5079309A (en) * | 1986-12-24 | 1992-01-07 | Amoco Corporation | Miscible blends of a poly(aryl ether ketone) and an imide containing polymer |
US4871817A (en) * | 1986-12-31 | 1989-10-03 | General Electric Company | Polyetherimide-liquid crystal polymer blends |
US4835047A (en) * | 1987-05-14 | 1989-05-30 | Avraam Isayev | Wholly aromatic polyester fiber-reinforced polyetherimide composite and process for preparing same |
DE3883950D1 (de) * | 1987-12-24 | 1993-10-14 | Pirelli General Plc | Ternäre Mischungen als Leistungsisolation. |
JPH01169567U (de) * | 1988-05-17 | 1989-11-30 | ||
DE3927399A1 (de) * | 1989-08-19 | 1991-02-21 | Hoechst Ag | Mehrkomponentenlegierungen mit einer glastemperatur |
DE59203848D1 (de) * | 1991-02-05 | 1995-11-02 | Hoechst Ag | Ternäre polymerlegierungen auf basis von polyaryletherketonen mit einer glastemperatur. |
US5145899A (en) * | 1991-02-28 | 1992-09-08 | E. I. Du Pont De Nemours And Company | Polymers modified by ketonic and ether-ketonic compounds |
US5364905A (en) * | 1991-04-26 | 1994-11-15 | The Goodyear Tire & Rubber Company | Process for the in-situ formation of reinforcing members in an elastomer and elastomer made thereby |
US5366663A (en) * | 1991-11-30 | 1994-11-22 | Hoechst Ag | Mixtures of liquid crystalline copolymers, polyether imides and compatibilizers and use thereof |
US5981007A (en) * | 1992-03-31 | 1999-11-09 | Foster-Miller, Inc. | Extruded thermoplastic, liquid crystalline polymers and blends thereof having a planar morphology |
EP0568917A1 (de) * | 1992-05-08 | 1993-11-10 | Hoechst Aktiengesellschaft | Mischungen aus Polyarylensiloxanen und amorphen Hochleistungspolymeren und deren Verwendung |
US6252011B1 (en) | 1994-05-31 | 2001-06-26 | Eastman Chemical Company | Blends of polyetherimides with polyesters of 2,6-naphthalenedicarboxylic acid |
US5439987A (en) * | 1994-05-31 | 1995-08-08 | Eastman Chemical Company | High heat deflection temperature blends of certain polyesters with polyetherimides |
US5520103A (en) * | 1995-06-07 | 1996-05-28 | Continental Carlisle, Inc. | Heat retentive food server |
US5852085A (en) * | 1996-12-31 | 1998-12-22 | General Electric Company | Transparent blends of polyetherimide resins |
KR20010101114A (ko) | 1998-12-02 | 2001-11-14 | 야스이 쇼사꾸 | 폴리이미드/폴리아릴레이트 수지조성물 및 그 성형체 |
US6150473A (en) * | 1998-12-14 | 2000-11-21 | General Electric Company | Polyetherimide resin/polyester resin blends having improved properties |
US7230066B2 (en) * | 2004-12-16 | 2007-06-12 | General Electric Company | Polycarbonate—ultem block copolymers |
US7655737B2 (en) * | 2006-11-16 | 2010-02-02 | Sabic Innovative Plastics Ip B.V. | Polycarbonate-polyester blends, methods of manufacture, and methods of use |
EP3083827B1 (de) * | 2013-12-18 | 2017-11-22 | SABIC Global Technologies B.V. | Polyester-/polycarbonatzusammensetzung und artikel |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4141927A (en) * | 1975-05-22 | 1979-02-27 | General Electric Company | Novel polyetherimide-polyester blends |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2057293A5 (en) * | 1969-08-11 | 1971-05-21 | Inst Elementoorganic | Polyimide anti-friction material |
JPS5614699B2 (de) * | 1972-12-02 | 1981-04-06 | ||
GB1523226A (en) * | 1975-10-15 | 1978-08-31 | Unitika Ltd | Resin composition and a process for preparing same |
US4171330A (en) * | 1977-01-27 | 1979-10-16 | Unitika Ltd. | Fire-retardant resin composition |
-
1979
- 1979-12-26 US US06/106,504 patent/US4250279A/en not_active Expired - Lifetime
-
1980
- 1980-12-16 CA CA000366912A patent/CA1157190A/en not_active Expired
- 1980-12-23 JP JP18144480A patent/JPS5699252A/ja active Granted
- 1980-12-23 EP EP80108183A patent/EP0033011B1/de not_active Expired
- 1980-12-23 AT AT80108183T patent/ATE13773T1/de active
- 1980-12-23 DE DE8080108183T patent/DE3070763D1/de not_active Expired
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4141927A (en) * | 1975-05-22 | 1979-02-27 | General Electric Company | Novel polyetherimide-polyester blends |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0097969A1 (de) * | 1982-06-30 | 1984-01-11 | Amoco Corporation | Plastifiziertes thermoplastisches Polymer |
EP0104659A2 (de) * | 1982-09-29 | 1984-04-04 | Amoco Corporation | Mischungen von Poly(etherimiden) und Polyamiden |
EP0104659A3 (en) * | 1982-09-29 | 1985-08-28 | Union Carbide Corporation | Blends of poly(etherimides) and polyamides |
EP0133236A2 (de) * | 1983-07-28 | 1985-02-20 | Bayer Ag | Thermoplastische Formmassen |
EP0133236A3 (en) * | 1983-07-28 | 1986-06-04 | Bayer Ag | Thermoplastic moulding compounds |
EP0594386A1 (de) * | 1992-10-23 | 1994-04-27 | General Electric Company | Duktile Mischungen von Polyestercarbonate oder Polyarylate mit Polyimidharzen |
US5387639A (en) * | 1992-10-23 | 1995-02-07 | General Electric Company | Ductile blends of polyester-carbonate or polyarylates and polyetherimide resins |
Also Published As
Publication number | Publication date |
---|---|
JPS6158091B2 (de) | 1986-12-10 |
JPS5699252A (en) | 1981-08-10 |
CA1157190A (en) | 1983-11-15 |
ATE13773T1 (de) | 1985-06-15 |
EP0033011B1 (de) | 1985-06-12 |
DE3070763D1 (en) | 1985-07-18 |
US4250279A (en) | 1981-02-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0033011B1 (de) | Mischungen von Polyarylaten und Polyetherimiden | |
EP0033394B1 (de) | Formmassen aus Poly(aryläther)harzen und Polyätherimidharzen | |
US4908418A (en) | Ternary polymer blends | |
US5521258A (en) | Autoclave resistant blends of poly(ester-carbonate) and polyetherimide resins | |
EP0037547B1 (de) | Formmassen und daraus hergestellte Formteile | |
US4923933A (en) | Polycarbonate/polyphthalate carbonate blends exhibiting good flame resistance | |
EP0402674B1 (de) | Verfahren zur Herstellung von Polycarbonat-Polysiloxan-Blockcopolymeren | |
JPH06200128A (ja) | ポリエステル‐カーボネートまたはポリアリーレートとポリイミド樹脂からなる延性のブレンド | |
EP0097969A1 (de) | Plastifiziertes thermoplastisches Polymer | |
EP0187416A2 (de) | Polyterephthalatcarbonat-Polyetherimid-Polyester-Mischungen | |
JPH0361703B2 (de) | ||
EP0618945A1 (de) | Flammenhemmende thermoverformbare mischungen aus copolymere harze. | |
US4532305A (en) | Thermoplastic polymer plasticized with a poly(aryl ether) | |
EP0114290A1 (de) | Formmassen aus Copolyester-Carbonaten | |
EP0117327A1 (de) | Ternäre Polymermischungen | |
US4510289A (en) | Polycarbonate/condensation polymer blends | |
US4746710A (en) | Shaped article formed from a blend of a poly(aryl ether) and a polycarbonate and/or a polyarylate | |
EP0186927A2 (de) | Polymermischungen, enthaltend ein Polyetherimid und ein Polyphthalatcarbonat | |
EP0418377A1 (de) | Verfahren zur herstellung von polykarbonat und/oder polyarylat-block-copolymeren mit poly(arylatäthern) | |
EP0704487A1 (de) | Polyestercarbonatabmischungen | |
CA1334707C (en) | Composition | |
EP0117326A1 (de) | Polyetherimiden-Polyarylaten-Mischungen | |
US5159028A (en) | Process for the preparation of polycarbonate and/or polyarylate block copolymers with poly(aryl ethers) | |
US4281088A (en) | Novel halobisphenolethylene polycarbonate-polyester blends | |
US5047486A (en) | Integrated process for the preparation of polycarbonate and/or polyarylate block copolymers with poly(aryl ethers) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Designated state(s): AT BE CH DE FR GB IT NL SE |
|
17P | Request for examination filed |
Effective date: 19810921 |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: UNION CARBIDE CORPORATION |
|
ITF | It: translation for a ep patent filed |
Owner name: ING. C. GREGORJ S.P.A. |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Effective date: 19850612 |
|
REF | Corresponds to: |
Ref document number: 13773 Country of ref document: AT Date of ref document: 19850615 Kind code of ref document: T |
|
REF | Corresponds to: |
Ref document number: 3070763 Country of ref document: DE Date of ref document: 19850718 |
|
ET | Fr: translation filed | ||
BECH | Be: change of holder |
Free format text: 850612 *AMOCO CORP. |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
ITPR | It: changes in ownership of a european patent |
Owner name: CESSIONE;AMOCO CORPORATION |
|
NLS | Nl: assignments of ep-patents |
Owner name: AMOCO CORPORATION TE CHICAGO, ILLINOIS, VER. ST. V |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PUE Owner name: AMOCO CORPORATION |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: 732 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: TP |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 19901120 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 19901121 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19901129 Year of fee payment: 11 |
|
ITTA | It: last paid annual fee | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19901231 Year of fee payment: 11 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Effective date: 19911224 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Effective date: 19911231 Ref country code: CH Effective date: 19911231 Ref country code: BE Effective date: 19911231 |
|
BERE | Be: lapsed |
Owner name: AMOCO CORP. Effective date: 19911231 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19920701 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee | ||
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19921110 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19921123 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19921127 Year of fee payment: 13 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19931223 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19931223 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Effective date: 19940831 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19940901 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
EUG | Se: european patent has lapsed |
Ref document number: 80108183.7 Effective date: 19920704 |